Complex reduction chemistry of (abpy)PtCl2, abpy = 2,2'-azobispyridine: formation of cyclic [(micro,eta2:eta1-abpy)PtCl]2(2+) with a new coordination mode for abpy and a near-infrared ligand-to-ligand intervalence charge transfer absorption of the one-electron reduced state.

The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand pi interaction as supported by DFT calculations. Unexpectedly, its chemical or electrochemical reduction occurs irreversibly to yield EPR-detectable [(micro,eta2:eta2-abpy)[PtCl2]2]*- and, as the main product of chloride dissociation, the structurally identified and DFT-calculated dinuclear [(micro,eta2:eta1-abpy)PtCl]2(2+) with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible one-electron reduction of that dimer, separated by 0.24 V, exhibits an intense near-infrared band for the monocationic intermediate [(abpy(-I))(abpy)Pt2Cl2]*+ at 1220 nm (epsilon = 3370 M(-1) cm(-1)) which is attributed to a ligand-to-ligand intervalence charge-transfer transition.

Multinuclear NMR study of some organoplatinum complexes containing multifunctional azines as chelating ligands.

1H-detected indirect NMR techniques were used to determine 15N and 195Pt NMR parameters for a series of organoplatinum(IV) complexes and one platinum(II) complex containing nitrogen-based azobispyridine, bispyridyltetrazine, and bipyrimidine ligands. The inverse technique permitted the detection of small 4J(Pt,H) and 5J(Pt,H) long-range couplings and the acquisition of 15N NMR data in natural isotopic abundance via nJ(N,H) intra- and inter-ligand couplings, but failed in cases where coherence transfer is quenched by rapid relaxation of the metal atom. In one case, analysis of satellite patterns in a set of 1H,15N, 1H,195Pt and 1H,13C correlation spectra allowed a positive sign to be determined for 1J(Pt,15N). Qualitative arguments are presented to explain the observed 15N coordination shifts in complexes with different azine ligands in terms of azine-M dative bond formation and LnM-azine back-donation.

Reduced and excited states of (bpym)[PtCl(2)](n)() (bpym = 2,2'-bipyrimidine; n = 1, 2): experiments and DFT calculations.

The complexes (bpym)PtCl(2) (1) and the new (micro-bpym)[PtCl(2)](2) (2), bpym = 2,2'-bipyrimidine, were synthesized and, in the case of 1, crystallized in solvent-free form for X-ray diffraction. The molecules 1 exhibit two different kinds of stacking motifs in the crystal with an interstack CH--N interaction. Complexes 1 and 2 were found to be sufficiently soluble for cyclic voltammetry, spectroscopy (absorption and emission), and spectroelectrochemical studies (UV-vis, EPR). As a result of single or double coordination of the strongly sigma-accepting [PtCl(2)] fragment to bpym, the paramagnetic anions 1(*)(-)() and 2(*)(-)() and the dianions 1(2-) and 2(2-) could be reversibly generated, despite the presence of metal-halide bonds. DFT calculations of A((195)Pt) and g tensor components confirm that the singly occupied MOs of the monoanionic species have mainly pi(bpym) character with nonnegligible platinum d orbital participation. The assignments of the electronic absorption and emission and resonance Raman spectra for both complexes are supported by DFT calculations.

Metalla-supramolecular rectangles as electron reservoirs for multielectron reduction and oxidation.

The electron-transfer capacity of molecular rectangle ions [Pt(II)(4)(PEt(3))(8)(mu-anth(2-))(2)(mu-L)(2)](4+) with anth = anthracene-1,8-diyl and L = 4,4'-bipyridine (bp) or 1,2-bis(4-pyridyl)ethene (bpe) was investigated in acetonitrile and dichloromethane using cyclic voltammetry, EPR, and UV-vis-near-IR spectroelectrochemistry. The compounds can be reversibly reduced, first in a two-electron process and then via two closely separated one-electron steps. Oxidation was also possible at rather low potentials in a reversible two-electron step, followed by an electrochemically irreversible process. The spectroscopic results indicate reduction at the neutral acceptor ligands L and oxidation at the formally dianionic anthracene "clips". In contrast, the prototypical molecular square ([Pt(triphos)(mu-bp)](4))(8+) undergoes only irreversible reduction.